Method for predicting fouling tendency of a hydrocarbon-containing feedstock

ABSTRACT

Disclosed herein is a method involving the steps of (a) precipitating an amount of asphaltenes from a liquid sample of a first hydrocarbon-containing feedstock having solvated asphaltenes therein with one or more first solvents in a column; (b) determining one or more solubility characteristics of the precipitated asphaltenes; (c) analyzing the one or more solubility characteristics of the precipitated asphaltenes; and (d) correlating a measurement of feedstock fouling tendency for the first hydrocarbon-containing feedstock sample with a mathematical parameter derived from the results of analyzing the one or more solubility characteristics of the precipitated asphaltenes.

PRIORITY CLAIM

This application is a continuation application of, and claims benefit ofand priority to, U.S. patent application Ser. No. 13/490,307, filed Jun.6, 2012, and U.S. patent application Ser. No. 13/490,316, filed Jun. 6,2012, each of which claims priority to and is a continuation applicationof U.S. patent application Ser. No. 13/243,782, filed on Sep. 23, 2011(published as publication number US 20120016168 on Jan. 19, 2012), whichis itself a continuation application of, and claims benefit of andpriority to, U.S. patent application Ser. No. 12/970,535, filed on Dec.16, 2010 (published as publication number US 20110120950 A1 on May, 26,2011) which itself is a continuation application of, and claims benefitof and priority to, U.S. patent application Ser. No. 11/510,491, filedAug. 25, 2006 (published as publication number US 2007/0048874 A1 onMar. 1, 2007 and issued as U.S. Pat. No. 7,875,464 B2 on Jan. 25, 2011)which itself is a United States non-provisional patent application andclaims benefit of and priority to U.S. provisional patent applicationSer. No. 60/711,599, filed Aug. 25, 2005, each said application herebyincorporated herein by reference in its entirety.

GOVERNMENT LICENSE RIGHTS

This application relates to work performed under US DOE CooperativeAgreement DE-FC26-98FT40322. The US government may have certain rightsin this inventive technology, including “march-in” rights, as providedfor by the terms of US DOE Cooperative Agreement DE-FC26-98FT40322.

BACKGROUND OF THE INVENTION

Generally, this inventive technology relates to substance analysisand/or processing. More specifically, the inventive technology, in atleast one embodiment, relates to in-vessel generation of a material froma solution of interest as part of a processing and/or analysisoperation. Preferred embodiments of the in-vessel material generation(e.g., in-vessel solid material generation) include precipitation; incertain embodiments, analysis and/or processing of the solution ofinterest may include dissolution of the material, perhaps as part of asuccessive dissolution protocol using solvents of increasing ability todissolve the material, in order to gain a desired amount of informationabout the solution of interest or to process a solution of interest asdesired. Applications include, but are by no means limited to estimationof a coking onset and solution (e.g., oil) fractionating.

SUMMARY OF THE INVENTION

The present inventive technology includes a variety of aspects which maybe selected in different combinations based upon the particularapplication or needs to be addressed. In one basic form, the inventivetechnology relates to in-vessel generation of a material (e.g., a solidmaterial) from a solution of interest (e.g., via precipitation), andperhaps dissolution of that solid material, as part of a processingand/or analysis operation. Advantages of the inventive technology relateto improvements in speed, efficiency, and accuracy, inter alia, relativeto known material processing and analysis methods.

Embodiments of the present invention may identify instrumental analysesthat could measure the amount of asphaltenes in fossil fuel materials orcorrelate with coking indexes and perhaps lead to the development of arapid analysis system.

It is therefore an object of certain embodiments of the presentinventive technology to provide a rapid on-column precipitation anddissolution method for rapid measurement of a cyclohexane solubleportion of asphaltenes precipitated from a hydrocarbonaceous solution ofinterest.

It is an object of certain embodiments of the present inventivetechnology to provide an automated system for rapid measurement of acyclohexane soluble portion of asphaltenes.

It is an object of certain embodiments of the present inventivetechnology to provide an in-vessel precipitation/dissolution system forimproved processing (including but not limited to fractionating) of asolution of interest.

It is an object of certain embodiments of the present inventivetechnology to provide an in-vessel precipitation/dissolution system forimproved analysis of a solution of interest (including but not limitedto determining the solution's makeup relative to dissolved materials ofdifferent polarity).

It is an object of certain embodiments of the present inventivetechnology to provide an automated analysis and/or processing methodusing in-vessel material generation.

Naturally, further objects, goals and embodiments of the inventions aredisclosed throughout other areas of the specification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a Separation Profile for 10 mg Redwater, B.C. Residuum on160×8.0 mm PTFE Column, 700 nm Absorbance Detector. Gradient: 0 min.Heptane, 2 min. Cyclohexane, 15 min. Toluene:methanol (98:2), 40 min.Heptane; 3.0 mL/min.

FIG. 2 shows a Sample Size Study with Redwater, B.C. Residuum on a 150mm×4.6 mm PTFE Column (2.5 cc Volume), 700 nm Absorbance Detector.Gradient: 0 min. Heptane, 1 min. Cyclohexane, 8 min. Toluene:methanol(98:2) (v:v), 14 min. Heptane; 2.0 mL/min.

FIG. 3 shows a Sample Size Study with Redwater, B.C. Residuum on a 100mm×7.0 mm PTFE Column (3.8 cc Volume), 700 nm Absorbance Detector.Gradient: 0 min. Heptane, 1 min. Cyclohexane, 10 min. Toluene:methanol(98:2) (v:v), 15 min. Heptane; 2.5 mL/min.

FIG. 4 shows a Sample Size Study with Redwater, B.C. Residuum on a 250mm×10 mm PTFE Column (20 cc Volume), 700 nm Absorbance Detector.Gradient: 0 min. heptane, 3 min. Cyclohexane, 13 min. Toluene:methanol(98:2) (v:v), 21 min. heptane; 2.5 mL/min.

FIG. 5 shows Separation of 2 mg (10 uL) Unpyrolyzed Boscan Residuum inToluene on 250 mm×10 mm PTFE Column, 500 nm Absorbance Detector.Gradient: 0 min. Heptane, 15 min. Cyclohexane, 30 min, Toluene:methanol(98:2), 40 min. heptane, 4.0 mL/min.

FIG. 6 shows a Separation of 2 mg (10 uL) Unpyrolyzed Boscan Residuum inToluene on 250 mm×10 mm PTFE Column with ELSD Detector. Gradient: 0 min.Heptane, 15 min. Cyclohexane, 30 min, Toluene:methanol (98:2), 40 min.Heptane, 4.0 mL/min.

FIG. 7 shows a Correlation of 500 nm Absorbance Detector and ELSD PeakAreas for Three-Solvent Separation with Values from GravimetricDetermination of Heptane Asphaltenes.

FIG. 8 shows a Separation of 2 mg (10 uL) Unpyrolyzed Boscan Residuum inCyclohexanone on 250 mm×10 mm PTFE Column, 500 nm Absorbance Detector.Gradient: 0 min. Heptane, 15 min. Cyclohexane, 30 min, Toluene, 40 min.Cyclohexanone, 50 min. Heptane, 4.0 mL/min.

FIG. 9 shows a Separation of 2 mg (10 uL) Unpyrolyzed Boscan Residuum inCyclohexanone on 250 mm×10 mm PTFE Column, ELSD Detector. Gradient: 0min. Heptane, 15 min. Cyclohexane, 30 min, Toluene, 40 min.Cyclohexanone, 50 min. Heptane, 4.0 mL/min.

FIG. 10 shows a Separation of 2 mg (10 uL) Unpyrolyzed Boscan Residuumin Methylene Chloride on 250 mm×10 mm PTFE Column, 500 nm AbsorbanceDetector. Gradient: 0 min. Heptane, 15 min. Cyclohexane, 30 min,Toluene, 40 min. Methylene chloride, 50 min. Heptane, 4.0 mL/min.

FIG. 11 shows a Separation of 2 mg (10 uL) Unpyrolyzed Boscan Residuumin Methylene Chloride on 250 mm×10 mm PTFE Column, ELSD Detector.Gradient: 0 min. Heptane, 15 min. Cyclohexane, 30 min, Toluene, 40 min.Methylene Chloride, 50 min. Heptane, 4.0 mL/min.

FIG. 12 shows a Relative Peak Areas for Four Original and PyrolyzedResidua in Cyclohexanone on 250 mm×10 mm PTFE Column, UV 500 nm Detector(top) and ELSD Detector (bottom). Gradient: 0 min. Heptane, 15 min.Cyclohexane, 30 min, Toluene, 40 min. Cyclohexanone, 50 min. Heptane,4.0 mL/min.

FIG. 13 shows a Relative Peak Areas for Four Original and PyrolyzedResidua in Methylene Chloride on 250 mm×10 mm PTFE Column, UV 500 nmDetector (top) and ELSD Detector (bottom). Gradient: 0 min. Heptane, 15min. Cyclohexane, 30 min, Toluene, 40 min. Methylene Chloride, 50 min.Heptane, 4.0 mL/min.

FIG. 14 shows a Correlation of 500 nm Absorbance Detector and ELSD PeakAreas for Four Solvent Separation with Cyclohexanone with Values fromGravimetric Determination of Heptane Asphaltenes.

FIG. 15 shows a Correlation of 500 nm Absorbance Detector and ELSD PeakAreas for Four Solvent Separation with Methylene Chloride with Valuesfrom Gravimetric Determination of Heptane Asphaltenes.

FIG. 16 shows a ELSD Separation Profile for 10 cc Methylene ChlorideBlank Injection

FIG. 17 shows a ELSD Separation Profile for 0.38 mg Boscan HeptaneAsphaltenes in 10 uL Methylene Chloride.

FIG. 18 shows a ELSD Separation Profile for 0.50 mg Unpyrolyzed BoscanResiduum Boscan in 10 uL Methylene Chloride.

FIG. 19 shows a Correlation Between Weight Percent GravimetricAsphaltenes and Weight Percent ELSD Polars from Two-Solvent Separation.

FIG. 20 show vessels as may be used in certain embodiments of theinventive technology, with sectional cutouts affording a view of packingmaterial, and material precipitated thereon.

FIG. 21 shows a schematic of components of an apparatus, includingchromatographic equipment, that may be used in certain embodiments ofthe inventive technology.

FIG. 22 shows a PTFE-packed stainless steel column in accordance withcertain embodiments of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As mentioned earlier, the present invention includes a variety ofaspects, which may be combined in different ways. The followingdescriptions are provided to list elements and describe some of theembodiments of the present invention. These elements are listed withinitial embodiments, however it should be understood that they may becombined in any manner and in any number to create additionalembodiments. The variously described examples and preferred embodimentsshould not be construed to limit the present invention to only theexplicitly described systems, techniques, and applications. Further,this description should be understood to support and encompassdescriptions and claims of all the various embodiments, systems,techniques, methods, devices, and applications with any number of thedisclosed elements, with each element alone, and also with any and allvarious permutations and combinations of all elements in this or anysubsequent application.

At least one embodiment of the inventive technology may be a method thatcomprises the steps of establishing a precipitant in a vessel (a column27 or a batch type vat 46, as but two examples) having a stationaryphase (lattice type or packing material 26, as but two examples)established therein; adding a solution of interest 31 (e.g., oil, or anyother material which one desires to process or analyze in any fashion)to the vessel; precipitating a material (e.g., a solid material, aviscous liquid material, and/or a gel material) from the solution ofinterest; and generating a remnant liquid upon performing the step ofprecipitating a material from the solution of interest. The step ofestablishing a precipitant (any material that effects precipitation) ina vessel may be performed by adding the precipitant (heptane, pentane,and/or isooctane, as but a few examples) to the vessel in liquid form,but indeed other methods (e.g., adding a powder form of the precipitantto the vessel and then adding a dissolving liquid) may be used. It is ofnote that any vessel used for large scale processing (as opposed toanalysis of a small sample such as an aliquot), is referred to as abatch type vessel.

The vessel may be a column or batch type vat (as but two examples).Typically, but not necessarily, a column would be used when the methodwere employed for solution analysis (measuring asphaltene content of anoil or estimating an onset of coking that might occur during processingof oil, as but two of many examples), and the batch type vat would beused when processing a solution (fractionating oil, as but one of manyexamples). The stationary phase (whether lattice, packing material, orother) may be substantially inert in that, e.g., it is designed suchthat there is no or minimal interaction, such as absorbance, of thestationary phase with the contacting solution or solute, in someembodiments. Such a substantially inert stationary phase includes but isnot limited to oligomers or polymers of polytetrafluorethylene, alsoknown as PTFE (Teflon), polyphenylene sulfide, silicon polymer,fluorinated polymers or elastomers (e.g., Vitons), or PEEK stationaryphase. However, in some embodiments, it may be desired that thestationary phase (whether lattice, packing material, or other) is notsubstantially inert (i.e., it is chemically interactive), and thatindeed it is selected such that there is some interaction between it andthe contacting liquid (whether solvent, solute, solution or other). Itis also of note that any of such stationary phases, whether packingmaterial or lattice, or other, need not be solid (e.g., need not besolid PTFE, e.g.), but instead can indeed be only coated with theindicated material. Packing material can be beaded, ground, chipped,small rods, pebbled, or blocked, as but a few examples—essentially ofany form that can be packed in a column.

One fact pointing to the non-obviousness of certain embodiments of theinventive technology is the precipitation of material on or within asubstantially inert stationary phase, as columnar liquid chromatographyrequires adsorption effects (i.e., “non-inertness”, or chemicalinteraction) between the stationary phase and passing substratesdissolved in solution for operation. It is also of note that for astationary phase to be established in a vessel, it certainly need not,but may, fill most of or all of the entire volume of the vessel.

The solution of interest added to the vessel in certain embodiments ofthe inventive technology may be oil or any other material which onedesires to process and/or analyze in any fashion (wine, water,biological fluids, as but a few examples). Indeed, one may desire todetermine information that relates more specifically to the asphaltenesin oil, tannins in wine, metals (or other impurities) in water, andproteins in biological fluids, as but a few examples. The precipitatedmaterial may be in (not presented mutually exclusively) powdered form,granular form, layered form, coated form, and/or lump form, as but a fewexamples; it may be solid, gel, and/or viscous liquid. Basically,certain dissolved solution constituent(s) may come out of solution uponthe solution's contact with the precipitant. Often, what is seen issolid material that coats the stationary phase, or portions thereof(e.g., it may precipitate within the packing bed). Of course, bymaterial generation is not meant the creation of new mass from nothing,but rather a generation of a gel, viscous liquid, and/or solid materialthat was not present before in such gel, viscous liquid, and/or solidform. It is of note that indeed, a gel and even a viscous liquid mayinclude solid material.

Typically, the precipitant will have a polarity that is sufficientlydifferent from the solution of interest so as to effect precipitation ofa material from the solution of interest. It is of note that theprecipitant may also be referred to as a precipitant solvent in thatthere typically will be a remnant liquid (e.g., a remnant solution)generated during the precipitation event; the term precipitant solventmay be appropriate in such instances because upon interaction of theprecipitant with the solution of interest, some material (e.g.,precipitant insoluble material) may be precipitated from the solutionwhile other material (e.g., precipitant soluble material) may remaindissolved in what, after the precipitation, may be referred to asremnant solution. In a situation where all of the dissolved material inthe solution of interest is precipitated, then what remains is a remnantliquid, not a remnant solution.

At least one embodiment of the inventive technology may comprise amethod comprising the steps of: establishing a precipitant in a columnof a liquid chromatograph apparatus (equipment typically used for liquidchromatography); adding a solution of interest to the column;intentionally precipitating a material in said column to yield a remnantliquid; and determining at least one characteristic of said solution ofinterest. Indeed, as those of ordinary skill in the art wouldappreciate, the step of intentionally precipitating a material (e.g.,solid, gel, and/or viscous liquid) in a liquid chromatograph column isentirely unconventional and counter chromatographic procedure in thatstandard liquid chromatographic protocol requires a mobile phase inwhich an added solution is entirely soluble; of course, the step ofintentionally precipitating is performed wherever the precipitation isnon-accidental (e.g., whenever it occurs as a result of an appropriateselection of material as a precipitant). Typically, in order toprecipitate, as is well known, polarities or other chemicalcharacteristics (acid/base interactions, chelation, chemical reaction,protein binding, etc.) of the precipitant and the solution out of whicha material is to be precipitated need to be sufficiently different.Embodiments covered by these methods include primarily analysis of thesolution of interest. Indeed, the step of determining at least onecharacteristic of a solution of interest is performed whenever any sortof analysis occurs (whether that analysis be of a dissolved materialsolution, of a precipitated material, a remnant solution, or othersubstance).

Examples of determining at least one characteristic include but are notlimited to the following: determining a coking index and determining asolution constituent amount (e.g., determining an amount of heptaneasphaltenes that are soluble in cyclohexane or other solvents,determining a height or area of a peak of a separation profile,determining a fractional amount of precipitated material, determining apolarity-based makeup of a solution). Such characteristics may be usefulin control of one or more of the following: oil processing, oilfractionating, oil production processes, pipeline fouling,hydrotreating, distillation, vacuum distillation, atmosphericdistillation, visbreaking, blending, asphalt formation, extraction,coking onset estimation and fouling, as but a few examples. It is ofnote that although an important application of embodiments of theinventive technology may be processes or analyses involvinghydrocarbonaceous materials (e.g., oil, in any of its many forms, suchas but not limited to crude oil), other materials may also be the“solution of interest” in inventive methods described herein. It is alsoof note that at times, it may be desired to determine a characteristicabout a material that is not in solution. In such cases, it may benecessary to first convert such material into solution form (e.g., byadding a solvent thereto) to generate a solution of interest so thatprocessing and/or analysis using the inventive methods described hereinmay be employed. Further of note is the fact that the term solvent is abroad term that includes “pure solvents” (e.g., straight methylenechloride), in addition to solvent mixtures.

As mentioned, certain embodiments may focus on processing of thesolution of interest. Such processing may include, but is not limitedto: fractionating the solution of interest (fractionating oil, as butone example), removing unwanted materials from the solution of interest,purification of the solution of interest, extraction of a constituent ofthe solution of interest, and preparing the solution of interest forfurther processing. Indeed, the solution of interest may be generatedupon adding a solvent to a material which one desires to process and/oranalyze. When such preparation is called for, the solution of interestis still processed and/or analyzed, even though the information gleanedtherefrom must perhaps thereafter be further manipulated to yieldinformation about the material itself (as opposed to the solution ofinterest).

At least one embodiment of the inventive technology may be an apparatusthat comprises a vessel adapted to allow passage of one or moresubstrates (e.g., any substances, including chemical solutions such as,but not limited to, oil) through at least a portion of the vessel; astationary phase either established in the vessel or configured forestablishment in the vessel; an inlet 40 to the vessel (through whichany of precipitant, solution of interest, and/or solvent may be added);and an outlet 41 from the vessel (through which any liquid (e.g.,dissolved material solution) may be removed from the vessel), where thestationary phase is substantially chemically inert relative to all ofthe one or more substrates that pass through at least a portion of thevessel and contact at least some of the stationary phase. The inlet andoutlet, particularly where it's an analytical system that is not purelygravity flow (e.g., where it uses high performance chromatographyequipment) may be anywhere on the vessel; perhaps, particularly innon-continuous flow systems, they are one in the same and controlled bya valve(s). A stationary phase is established in the vessel when it issituated in the vessel in any manner; for example, packing material 42may be packed in the vessel and/or a lattice 43 may be situated in thevessel, in some manner.

A stationary phase is configured for establishment in the vessel when,e.g., it is not provided in the vessel, but instead is in any form thatenables it to be established in the vessel. For example, packingmaterial is typically readily establishable in a vessel, as it may besimply placed (e.g., poured) into the vessel, and perhaps also packeddown. A lattice type stationary phase is configured for establishment inthe vessel when it can be, perhaps after some re-configuration by anoperator, placed in the vessel. It is of note that an inlet to thevessel may be quite large in certain circumstances (e.g., an “open”upper end that a batch type vat may have); of course, it may also besmaller (e.g. particularly as it may be in the case of a column). Theoutlet may be simply a passage through which material may be removedfrom the vessel, whether permanently open or openable/closeable.Particularly in a batch type system, the outlet may be anopenable/closeable drain (e.g., a stopcock).

Also worthy of mention is that in certain columnar embodiments of theinventive technology, the column need not be vertical. Indeed, thecolumn may be established to have any spatial orientation (vertical,horizontal, tilted, etc.) Gravity flow columnar embodiments may involve“off-horizontal” oriented columns; typically, a gravity flow columnwould be vertically situated. However, many embodiments, particularlythose using high performance chromatography equipment (where the columnis internally pressurized in significant manner), may involve a column(or other vessel) exhibiting any orientation. It is also of note that inparticular embodiments, certain columns may be adapted for use withchromatography equipment. Simply, as such, they may be used as part of achromatograph apparatus.

The stationary phase, whether lattice, packing material, or other, may,in some embodiments, be substantially inert (e.g., chemically inert)relative to all of the one or more substrates (substances) that passthrough at least a portion of the vessel and contact at least some ofthe stationary phase. Such an inert stationary phase may improveanalysis and processing in that the precipitate (at least a portion ofwhich typically precipitates directly onto the stationary phase) doesnot then chemically interact as is observed with a “non-inert”stationary phase. It is important to understand that the term inert, atthe least, includes inert relative to those substrates that thestationary phase will contact. As such, for example, a material that ischemically interactive with only a small group of compounds (i.e., notinert relative to such compounds) is still considered inert relative tothis inventive technology if such small group of compounds is not tointeract with the stationary phase. It is also of note that the terminert, or substantially inert (as opposed to the term completely inert)allows for a small, minimal degree of interaction between the stationaryphase and any of the substrates that contact it, as complete inertnessis difficult, if not impossible to achieve in some cases. Substantiallyinert may include causing reactions that impair results—whetheranalytical or processing—to an acceptable degree. Glass bead packingmaterial, for example, may not be considered a substantially inertstationary phase. In some applications (e.g., some biological assayrelated applications), an inert packing material may not be desirable,and a packing material that interacts with one or more constituents maybe desirable.

At least one embodiment of the inventive technology may be a method thatcomprises the steps of: adding a solution of interest to a vessel havingstationary phase established therein; generating a solid material insaid vessel and from the solution of interest; generating a remnantsubstance upon performing the step of generating a solid material;establishing a solvent in the vessel so that it contacts the solidmaterial; and dissolving at least a portion of the solid material togenerate a dissolved material solution. The step of generating a solidmaterial in the vessel and from the solution of interest includes, butis not necessarily limited to, precipitating a solid material from thesolution of interest (e.g., precipitating an asphaltene). It is also ofnote that the remnant substance, in the case of precipitation, is aremnant liquid. Establishing a solvent in the vessel (e.g., adding asolvent to the vessel) so that it contacts the solid material will, ofcourse, dissolve at least a portion of the solid material, if thesolvent added does indeed have a greater power to dissolve the solidmaterial than does the precipitant that effected, at least in part, itsgeneration. It is of note that even though what may coat a stationaryphase appears strictly gelatenous, indeed solid material makes up atleast part of the gel appearing material.

Given the general rule that like dissolves like (i.e., a substance of afirst polarity will dissolve a substance of a second polarity wheretheir polarities are sufficiently similar), if the precipitated materialis of high polarity (e.g., asphaltenes of oil), then the solvent(s)should be of higher polarity than the precipitant. If successivetreatments with different solvents are to be added to the vessel todetermine which amounts are soluble in that solvent, then later addedsolvents should have a polarity that is closer to that of theprecipitated material than earlier added solvents. Such is the reasoningbehind one (of many) successive asphaltene dissolution protocol—heptaneis first used as the precipitant, then the solvent cyclohexane is used,then toluene is used, and then methylene chloride is used (perhaps todissolve all remaining precipitated material). In such protocol, eachsuccessive solvent is of higher polarity. It is also of note that theprecipitant may be chosen such that it has a polarity that is less thansome constituent(s) of the solution of interest, while at the same timegreater than other constituent(s) of the solution of interest.

Successive dissolution protocols may involve the step of successivelydissolving at least one additional portion (e.g., in addition to thatdissolved by the first non-precipitating solvent) of the generatedmaterial with at least one additional solvent to generate at least oneadditional dissolved material solution. Of course, as mentioned, it istypically necessary to separate the existing dissolved material solutionfrom a space contacting the generated material so that the subsequentsolvent can then dissolve at least an additional portion of thegenerated material (at some point, a solvent may dissolve all of theremaining generated material). Much information may be gleaned from thesolution of interest upon analysis of un-dissolved generated material,or of the additional dissolved material solution.

In certain embodiments of the inventive technology, a solvent may beestablished in the vessel so that it contacts the generated material(such contact is observed whenever any dissolution occurs). Wheneverdissolution of the generated material occurs, a dissolved materialsolution is generated. Such solution may be analyzed, as mentioned,perhaps with a detector 22, thereby determining a characteristic (byproviding any information whatsoever about the solution of interest). Ofcourse, such analysis may be accomplished through the use of any of anumber of detectors employing evaporative light scattering, massspectrometry, conductivity, oxidation/reduction, refractive index,polarimetry, atomic spectroscopy, optical absorbance, x-ray, ultrasound,and/or fluorescence, as but a few of the available techniques. Suchdetection may occur as the analyzed substance leaves the vessel, whileit is in the vessel, or after it leaves the vessel. A typical setup of adetector may be not dissimilar to that found in some liquidchromatography set-ups, where the detector detects liquid as it elutesfrom the column (in the case of columnar, analytical embodiments), or asit is drained from a batch type vat (e.g., as in the processingembodiment).

Of course, as mentioned, in successive dissolution protocols, it may bedesired to add an additional solvent to further characterize (to gathermore information about) the solution of interest. Thus, it may benecessary to separate the liquid contacting the generated material(whether that liquid be a remnant liquid or a dissolved materialsolution) so that the subsequent solvent can be established such that itcan further dissolve the generated material. Typically, but notnecessarily, such “separating” step includes removing the liquidcontacting the generated material from the vessel. Further, “separating”includes “removing”, in addition to including “replacing”, as where theaddition of one liquid into a space occupied by a first liquid forcesthat first liquid out. Dissolved material solution may be acted upon bya detector 22; removed dissolved material solution 28 may be contained.It is of note that the term material refers not only to the materialimmediately after precipitation (or other type of material generation),but also to generated material that may remain after dissolution,whether one time or successively.

It is of note that some methods, especially analytical methods, mayinvolve continuous flow systems. As such, at least one liquid may beflowing from the vessel, under pressures that are greater than ambient(e.g., pump pressure effected by pump 32), at any time. Although indeedprocessing embodiments may involve continuous flow, typically, but notnecessarily, a solution processing method, and the batch type vat thatmay find use in such method, will not be continuously flowing; instead,such processing may involve only gravity flow, and the outlet from thevessel may indeed be closed at least some time during operation. Anytype of system may be internally pressurized (especially continuous flowsystems); pressures may be any that do not break system components andprovide acceptable (e.g., sufficiently accurate when analyzing) results.Internal pressures used in the experimental testing includes 50-500 psi,but highly pressurized systems (e.g., up to 12,000 psi) may also beused. Such systems (or indeed other systems), whether continuous flow ornot, may include a solvent selection valve 29.

Those methods, whether analytical or processing, involving successivedissolution, afford considerable opportunity to characterize thesolution of interest. Indeed, for certain applications, it may only benecessary to simply generate a material in the vessel (e.g., byprecipitation), and then analyze the material and/or the remnantsubstance (e.g., remnant liquid). But in some applications, moreinformation about the solution of interest may be desired; suchadditional information may be acquired upon the afore-describedsuccessive dissolution protocol. Such additional information, whetherstemming from a separation profile 21 (e.g., peak values, such as peakheights, peak sharpness, and peak areas, and ratios thereof; timesuntil, between or during elution(s), absence of peaks, sharpness ofpeaks, etc.) or from other data, can be, if required, mathematicallymanipulated (in a manner well known in the art) to provide even moreinformation, thereby enabling even greater control over all types ofoperations.

EXPERIMENTS AND RESULTS THEREOF Summary

Through a series of experiments, an automated separation technique wasdeveloped that provides a new approach to measuring the distributionprofiles of the most polar, or asphaltenic components of an oil, using acontinuous flow system to precipitate and re-dissolve asphaltenes fromthe oil. Indeed, at least some of the embodiments of the inventivetechnology may be automated such that the solution of interest, theprecipitant 24, and solvent(s) 25 are added (e.g., injected by injector30) to the vessel (and perhaps removed therefrom) automatically.Characteristics of the solution of interest may be determinedautomatically also, perhaps using a detector configured (e.g.,programmed) to detect and record during elution or at other appropriatetime. Methods of analysis based on this new technique were developed.Many of the techniques used below can be applied to the analysis and/orprocessing of materials other than oil.

About 37-50% (w/w) of the heptane asphaltenes from unpyrolyzed residuadissolve in cyclohexane. As pyrolysis progresses, this number decreasesto below 15% as coke and toluene insoluble pre-coke materials appear.This solubility measurement can be used after coke begins to form,unlike the flocculation titration, which cannot be applied tomulti-phase systems. Currently, the procedure for the isolation ofheptane asphaltenes and the determination of the amount of asphaltenessoluble in cyclohexane spans three days.

A more rapid method to measure asphaltene solubility was explored usinga novel on-column asphaltene precipitation and re-dissolution technique.This was automated using high performance liquid chromatography (HPLC)equipment with a step gradient sequence using the solvents: heptane,cyclohexane, and toluene:methanol (98:2). Results for four series oforiginal and pyrolyzed residua were compared with data from thegravimetric method. The measurement time was reduced from three days toforty minutes. The separation was expanded further with the use of foursolvents: heptane, cyclohexane, toluene, and cyclohexanone or methylenechloride. This provides a fourth peak which represents the most polarcomponents, in the oil. A method which uses a two solvent step gradient:heptane and methylene chloride, was explored also. A calculation basedon the percent area of the second peak relative to the total area ofboth peaks correlates well with gravimetric asphaltene content.Gravimetric heptane asphaltenes typically can be isolated from an oilonly after the polar material represented by the second peak exceeds aminimum threshold value in the oil sample. Methods based on the newon-column precipitation and re-dissolution technique providesignificantly more detail about the polar constituents of an oil thandoes the determination of gravimetric asphaltenes.

In particular embodiments, the present invention may provide explorationof rapid measurements of asphaltene solubility perhaps using anon-column material precipitation and dissolution technique. Measurementsmay be automated perhaps using liquid chromatography equipment (e.g.,high performance liquid chromatography (“HPLC”) equipment), perhaps witha step gradient sequence using solvents of increasing solvent strengthsuch as but not limited to heptane, cyclohexane, toluene:methanolmixtures and the like. Results using a column packed with ground PTFEstationary phase for an original and pyrolyzed residuum may correlatewell with data from a gravimetric method, and a measurement time may bereduced from about three days to perhaps less than three days such asbut not limited to about thirty minutes. As adsorption effects may beobserved with non-inert stationary phase, some embodiments focus on theuse of substantially inert stationary phase; however, the inventivetechnology is not limited to methods using only substantially inertstationary phase. In certain embodiments, a stainless steel columnpacked with ground PTFE may be used to provide a substantially inertmatrix perhaps with minimal adsorption characteristics for a separationto determine an amount of heptane asphaltenes and an amount of theasphaltenes that dissolve in cyclohexane. Methods can, inter alia, beused to provide a rapid direct measurement of the heptane asphaltenescontent of oil, asphalt or the like. The inventive techniques alsooffers the possibility of developing preparative or process levelseparations of petroleum materials to remove polar materials to generatean improved quality feed for subsequent processing. Of course, theexperiments and the results presented herein are in no way intended tolimit the scope of the inventive technology.

EXPERIMENTAL BACKGROUND

Petroleum residua consist of a continuum of associated polar asphaltenecomplexes dispersed in a lower polarity solvent phase by intermediatepolarity resins. When the residuum is heated to temperatures above 340deg C. (650 deg F.), the ordered structure is systematically andirreversibly destroyed, leading to coke formation following an inductionperiod. An important consideration in the refining industry is to beable to measure how close a pyrolyzed material is to forming coke on thecoke induction period timeline. Undesired coking during distillationresults in significant down time and economic loss. To avoid thisproblem, conservative heating profiles are often used, which results inless than optimal distillate yield, and less profitability. Theproximity to coke formation can be measured using the WRI CokingIndexes, which are calculations based on flocculation titration data orthe solubility of heptane asphaltenes in cyclohexane (Schabron et al.2001a, 2001b). As an example, coking indexes are discussed in U.S. Pat.No. 6,773,921, hereby incorporated hererin by reference. The CokingIndex values decrease during pyrolysis to a threshold value below whichcoke formation begins. Currently, the Coking Indexes require lengthylaboratory analysis of a residuum sample. A new, rapid on-columnprecipitation and re-dissolution method for rapidly measuring thecyclohexane soluble portion of asphaltenes was developed in the currentstudy.

The Solvation Shell Coking Index

Some aspects of the ordered structure of petroleum residua can bemodeled by the Pal and Rhodes suspended particle solution model ofdispersed solvated particles in a solvent matrix (as discussed in Paland Rhodes, 1989, Viscosity/Concentration Relationships of Emulsions,Journal of Rheology 33 (7) pp. 1021-1045, and Schabron et al. 2001c,each hereby incorporated by reference). The volume fraction of the coreof particles can be considered as the volume fraction of heptaneasphaltenes Φ. The volume of the core is increased by a solvation shellterm K_(S). Several solvated shells bind a portion of solvent andincrease the effective particle volume by a term K_(F). The term K_(S)K_(F) is called the solvation constant K. The effective particle volumeΦ_(EFF) is equal to the core asphaltene fraction volume increased by thesolvation terms as shown by the following equation:Φ_(EFF) =KN _(a) =K _(F) K _(S) N _(a)

The volume fraction of polar asphaltene cores, Φ_(a) can be estimatedfrom the mass fraction of heptane asphaltenes X_(a) divided by anassumed density of 1.2 g/cm³. K_(S) values for unpyrolyzed residua andasphalt systems are typically near or above 1.6. For pyrolyzed oils theK_(S) values decrease as pyrolysis progresses and the protective shellsurrounding the polar asphaltene core is destroyed (Schabron et al.2001a). A method for estimating K_(S) is to measure the mass fraction ofheptane asphaltenes that dissolve in cyclohexane (Y) using the equationbelow.K _(S)=1/(1−Y)

The above equation assumes that the density of the asphaltenes thatdissolve in cyclohexane is essentially the same as the density of theinsoluble portion.

Rapid Measurement of Cyclohexane Soluble Asphaltenes:

The K_(S) term is a Coking Index value that we have found to beuniversally applicable to vacuum or atmospheric residua or wholevisbroken oils. To obtain this value the amount of heptane asphaltenesthat dissolve in cyclohexane is measured. For unpyrolyzed residua, about37-50% (w/w) of heptane asphaltenes dissolve in cyclohexane. Thiscorresponds to K_(S) values of 1.6-2.0. As pyrolysis progresses, theamount of heptane asphaltenes soluble in cyclohexane decreases below 15%as coke and toluene insoluble pre-coke materials appear, whichcorresponds to K_(S) values below 1.2. This is an indicator of thedestruction of the intermediate polarity, or resins material. Anunstable system results when the depletion of the resins disables theability of the asphaltene/resin complexes to self-adjust their apparentmolecular weights to closely match the solubility parameter of thematrix. At that point on the coke formation induction time line, theordered system breaks down and the polar asphaltene material is nolonger stabilized, and coke begins to form (Schabron et al. 2001a,2001b).

Residua:

The four residua studied were Boscan, Lloydminster, and Redwater, B.C.from prior work at Western Research Institute (WRI), and MaxCL2 providedby ConocoPhillips.

Determination of Asphaltenes:

Heptane asphaltenes were isolated by heating an excess (40:1 v:w)mixture of reagent-grade n-heptane and residuum to 70 deg C. (158 degF.) for about ½ hour on a heated stir plate while stirring with amagnetic stir bar. This was followed by overnight stirring at roomtemperature. The following morning, the stirring was stopped for 30minutes prior to vacuum filtration using Ace, 140-mL, 10-20 micron,sintered glass filters. Residual solvent was removed from theasphaltenes on the filters using a vacuum oven set at 120 deg C. (248deg F.) for 30 minutes. The asphaltenes were cooled in a desiccatorprior to weighing.

A portion of n-heptane asphaltenes was ground to a fine powder using amortar and pestle. A 0.5-g portion of this was weighed into a 120-mLjar, and 100 mL of reagent grade cyclohexane and a magnetic stir barwere added. The mixture was stirred overnight. The mixture was allowedto settle for 30 minutes prior to vacuum filtration using Ace, 140-mL,10-20 micron, sintered glass filters. Solvent was removed from thefiltrate by rotary evaporation, and traces of cyclohexane were removedin a vacuum oven at 100 deg C. (212 deg F.) for 15 minutes. Thecyclohexane soluble materials were cooled in a desiccator prior toweighing.

Pyrolysis:

Pyrolysis experiments were performed at various residence times with500-g residua samples in a 4-inch diameter reactor with continuousstifling and distillate removal using a condenser at atmosphericpressure. Residua were evaluated as atmospheric bottoms material withoutdistillate. Coke and pre-coke materials were determined as tolueneinsolubles (TI) retained on a 10-micron filter.

On-Column Asphaltene Precipitation:

The on-column asphaltene precipitation and re-dissolution experimentswere conducted using a Waters 717 autosampler, a Waters 60F pump with600 controller, a Waters 1487 ultraviolet/visible absorbance detector,and an Alltech ELSD 800 detector. Elution solvents were reagent grade,with step gradients between solvents. Solutions of residua andasphaltenes were injected. Peak area integration was performed using aChrom Perfect Spirit 5.5 data system. Various columns and conditionswere tested. Pyrolyzed sample solutions were filtered through a 0.45micron PTFE filter prior to injection. ELSD separation peak areas werecorrected for small blank peaks due to the step gradient solventchanges.

Experimental Results

A new automated separation technique was developed that provides a newapproach to measuring the distribution profiles of the most polar, orasphaltenic components of an oil, using a continuous flow system toprecipitate and re-dissolve asphaltenes from the oil.

The Manual Method:

To measure the amount of asphaltenes using the manual method, a sampleof oil is weighed and mixed with an excess (30:1 ratio or greater, asbut one example) of aliphatic hydrocarbon solvent such as heptane. Themixture is stirred overnight, and the asphaltenes precipitate while themaltenes remain in solution. The mixture is then filtered and theprecipitate is rinsed repeatedly with the hydrocarbon solvent until thefiltrate is clear. The precipitate is then dried thoroughly, usually ina vacuum oven, and weighed. This procedure usually takes about 24 hours.To determine the cyclohexane soluble portion of the asphaltenes, theprecipitate is ground manually, and a portion of the ground precipitateis stirred overnight with an excess of cyclohexane. The next day, themixture is filtered to separate the cyclohexane soluble and insolubleportions. The full manual method to determine asphaltenes and thecyclohexane soluble portion of asphaltenes can take up to 3 days tocomplete.

The Automated Separation Method:

The new on-column separation provides a rapid method using an automatedcontinuous flow system. Bodusynski et al (1982, 1987) reportedgravimetric on-column dissolution methods for separating coal liquidsand petroleum residua deposited onto various packing materials usingsequential dissolution into various solvents. Solutions of sample weredirectly added to column packing material and the solvent was removed byevaporation outside the column. The packing material coated with samplewas then poured into a column. Sequential dissolution with a series ofsolvents of increasing polarity has also been performed on petroleumresidua materials without the use of a column (Schabron et al. 2001b).

The current technique involves on-column precipitation into a lowpolarity solvent mobile phase combined with subsequent re-dissolutionusing one or more solvents of increasing solvent strength and polarity.Although high performance liquid chromatography (HPLC) equipment isused, the separation does not involve a chromatographic separation basedon adsorption. A weighed portion of oil is dissolved in a solvent ofsufficient strength to dissolve the entire sample. An aliquot of thesolution is injected onto a column packed with granular (PTFE). In atleast one experiment, the initial solvent in the column and the solventinto which the sample solution is injected is heptane. Once the samplesolution enters the column with the heptane mobile phase, the heptanedisplaces and dilutes the injected solvent, and heptane insolublematerials precipitate. The soluble maltenes continue to move with theheptane and they elute from the column. The solvent is then switched toa stronger solvent, or a series of stronger solvents of increasingsolvent strength, which dissolves a portion or all of the precipitatedmaterial. The solvent is then switched back to heptane in preparationfor the next sample injection. Another injection is then made by theautosampler, and the cycle is repeated. Since the elution solvents arebeing changed, a refractive index detector can not be used. An opticalabsorbance detector can be used; however, there is some variation in theabsorptivities between asphaltenes from different residua, pyrolyzed andunpyrolyzed asphaltenes, and the cyclohexane soluble and insolubleportions of asphaltenes. In the current study, the use of an evaporativelight scattering detector (ELSD), which responds more uniformly to agiven number of molecules of each of the above materials, wasestablished. The result provides a powerful new automated tool forprocess control and heavy oil evaluation.

Pyrolysis:

Pyrolysis experiments were performed with the four residua to provideadditional pyrolyzed atmospheric bottoms samples for different pyrolysistimes at 400° C. The amounts of heptane asphaltenes andtoluene-insoluble materials in the original and pyrolyzed residuamaterials are provided in Table 1. Also provided are the calculatedK_(S) values. The K_(S) values for the four unpyrolyzed residua are all1.6 or larger, indicating that the residua are far from producing cokeon the coke formation induction time line. The data in Table 1 show thecharacteristic decrease in the K_(S) Coking Index values as pyrolysisprogresses. There are no toluene insoluble materials greater than 10microns in size in any of the product oils except for the 90-minuteBoscan oil and the 75-minute Redwater, B.C. which were pyrolyzed beyondthe coke formation threshold.

On-Column Asphaltene Precipitation Optimization Experiments

Experimental conditions were explored to optimize a single set ofseparation conditions for comparing various original and pyrolyzedresidua. The optical absorptivities of heptane asphaltenes, and thecyclohexane soluble and insoluble components of heptane asphaltenes intoluene solution for original and pyrolyzed residua for wavelengthsranging from 400 nm to 700 nm were evaluated. The purpose of theseexperiments was to determine the wavelength at which the absorptivitiesshowed the least variation between the different materials. Resultsshowed that the shorter wavelength (400 nm) provides more uniformabsorptivities than the higher wavelength (700 nm). Wavelengths below400 nm were not considered due to the strong absorbance of toluene.Although the results indicate that the shorter wavelength of 400 nmshould be used, the absorbance for some of the samples was too high atthis wavelength for the sample amounts injected in some developmentwork. Therefore, 700 nm was selected for the certain stages of the work.It is important to note in the discussions that follow that onlymaterials that absorb light at 700 nm are being detected. Saturatedaliphatic, naphthenic, and aromatic structures that do not exhibit browncolor in the visible region are not detected.

Separation Considerations:

Over the course of the development work, several important aspects tothe separation were better understood. For example, the separationtemperature can be near ambient and it does not need to be controlledexactly. In those embodiments where inertness is desired, glass wool orglass beads should not be used since they result in strong adsorptioneffects. The amount of sample injected should be maximized to minimizeadsorption effects, while the amount of solvent injected should be keptat a minimum. Peaks must be resolved well, despite some tailing which isdue to continuous re-dissolution of small amounts of materialprecipitated on the packing. The solvent flow rate must be compatiblewith the ELSD (in this case <6 mL/min). Since some pyrolyzed samplesresult in off-scale asphaltene peaks at 400 nm when 2 mg sample portionsare injected, a wavelength of 500 nm was selected for the absorbancedetector. Blank correction is required for the ELSD peak areas sincesmall, repeatable peaks are observed when the solvents are changed.

Sample Amount Injected:

The amount of sample injected and the column size to be used areimportant variables. FIG. 1 shows an initial separation profile at 700nm for unpyrolyzed Redwater, B.C. residuum obtained early in this study.Although the separation looks good, the resolution between peaks is notoptimal. Also, this particular column size is no longer available. Aseries of systematic experiments was subsequently performed to betterunderstand the effect of column size, volume injected, and sample amountinjected. The study also explored any differences that might occur ifeither toluene or decalin were used as the sample solvent. FIGS. 2-4show the peak areas for the total asphaltenes (cyclohexane soluble pluscyclohexane insoluble) as a function of amount injected for threedifferent stainless steel column sizes, each packed with 0.25-0.42 mmPTFE stationary phase. The results indicate that the separationconditions are easier to control with the larger column, and that at alow injection volume (<50 uL), toluene can be used as the samplesolvent. This is an important finding since residua samples dissolve intoluene much faster than in decalin.

Three Solvent Separation Conditions:

The separation conditions that were established for sample analysisusing the initial three solvent system are listed below.

-   -   1. 250×10 mm stainless steel column (Alltech 96511)    -   2. 0.25-0.42 mm PTFE stationary phase    -   3. Solvent flow rate: 4 mL/min    -   4. Step gradient times: 0 min. heptane, 15 min. cyclohexane, 30        min, toluene:methanol (98:2) (v:v), 40 min. heptane.    -   5. Sample solutions: 20 wt. % in toluene    -   6. Amount injected: 10 uL (2 mg)    -   7. Optical absorbance detector at 500 nm    -   8. Evaporative light scattering detector (ELSD) at 60° C. and        1.5 bar nitrogen

Three Solvent Separation Results:

Separation profiles for 10 uL of 20 wt. % unpyrolyzed Boscan residuum intoluene using an absorbance detector at 500 nm and an ELSD are providedin FIGS. 5 and 6, respectively. A comparison of K_(S) values determinedgravimetrically with K_(S) values determined by the new on-columnprecipitation and re-dissolution method is provided in Table 2 for aseries of original and pyrolyzed residua. Results show that the ELSDdata closely track the gravimetric data. K_(S) values decrease withpyrolysis severity for all four residua. The results for the 500 nmabsorbance detector show a similar trend of decreasing K_(S) values withincreasing pyrolysis times; however, the absolute values tend to besomewhat smaller than the corresponding gravimetric or ELSD values. Thisis due to the relatively lower optical absorptivity at 500 nm for thecyclohexane soluble portion of asphaltenes as compared with thecyclohexane insoluble materials. Both the Boscan 50-minute and theRedwater, B.C. 75-minute pyrolysis product oils contained some insolublematerial when the 20 wt. % in toluene solutions were pre-filteredthrough a 0.45 micron PTFE syringe filter prior to injection. Therefore,it is assumed that not all of the most polar material is being accountedfor in the separation profiles for these materials.

Gravimetric wt. % heptane asphaltenes and the total asphaltenes peakareas (cyclohexane plus toluene:methanol (98:2)) are listed in Table 3.The total areas of both the cyclohexane soluble and cyclohexaneinsoluble asphaltene peaks are plotted against the gravimetric heptaneasphaltene content in FIG. 7. ELSD data show a plateau for the severelypyrolyzed oils. This is probably due to the deposition of pre-cokematerial onto the PTFE stationary phase. This material is not recoveredby elution with toluene:methanol (98:2) (v:v). The purpose of the smallamount of methanol in this solvent mixture is to minimize the risk ofpolar normal-phase adsorption effects. Despite this precaution, the PTFEstationary phase in the first inch of the column is stained with a browncolored material after many sample injections, especially if the samplesconsist of severely pyrolyzed oils. Since the stationary phase is inertPTFE, the material is probably not adsorbed, but rather deposited on thepacking. Experiments showed that this brown colored material readilydissolves in methylene chloride. Toluene insoluble pre-coke material isexpected to be soluble in solvents with three-dimensional Hansensolubility parameter component values similar to those of methylenechloride, tetrahydrofuran, and quinoline (Table 4) (Hansen 2000). Theseparation was modified further to add a stronger solvent to dissolvethis toluene-insoluble material, to provide a fourth “pre-coke” peakusing a solvent with three-dimensional Hansen solubility parametervalues near that of methylene chloride. This is described in thefollowing section.

The 500 nm peak area show a general correlation with the heptaneasphaltene gravimetric data (FIG. 7). The plateau observed with the ELSDfor the same separation is still present, but not as evident. This isprobably due to the increase in absorptivity for the pyrolyzedasphaltenes material at 500 nm compared with the unpyrolyzed material.Thus, the deposition of a portion of this material onto the stationaryphase or loss in the sample filtration step would not be as evident withthe optical absorbance detector.

Four Solvent Separation Conditions:

The separation conditions that were established for sample analysisusing the four solvent system are listed below.

-   -   1. 250×10 mm stainless steel column (Alltech 96511)    -   2. 0.25-0.42 mm PTFE stationary phase    -   3. Solvent flow rate: 4 mL/min    -   4. Step gradient times: 0 min. heptane, 15 min. cyclohexane, 30        min. toluene, 40 min. solvent four (cyclohexanone or methylene        chloride), 50 min. heptane.    -   5. Sample solutions: 20 wt. % in cyclohexanone or methylene        chloride    -   6. Amount injected: 10 uL (2 mg)    -   7. Optical absorbance detector at 500 nm    -   8. Evaporative light scattering detector (ELSD) at 110° C. and 5        bar nitrogen for cyclohexanone series or 75° C. and 2.5 bar for        methylene chloride series

Four Solvent Separation Results:

From the list of polar solvents with similar Hansen solubilityparameters listed in Table 4, two candidate solvents were selected forthe four-solvent separation experiments. These were cyclohexanone andmethylene chloride. Cyclohexanone does not contain a halogen, and has aboiling point of 155° C., which is much lower than that of Quinoline(237° C.), so it can be used with the ELSD detector. Our observations inthe past have been that there are insoluble components present whensolutions of asphaltenes are made up in pyridine, so this solvent wasnot considered. Tetrahydrofuran is known to be unstable and veryreactive, so this also was not considered. Methylene chloride has a lowboiling point of 40° C., and is a very good solvent for asphaltenes. Adisadvantage is that it contains a halogen, and waste solvent from theseparation must be disposed of in a halogenated waste stream.

Solutions of 20 wt. % of the original and pyrolyzed residua wereprepared in both cyclohexanone and methylene chloride. It takes aminimum of 2 hours for some pyrolyzed samples to fully dissolve incyclohexanone, even with agitation in an ultrasonic bath. The samplesdissolved within 15 minutes in methylene chloride.

Separation profiles for 10 uL of 20 wt. % unpyrolyzed Boscan residuum incyclohexanone with cyclohexanone as the fourth solvent using anabsorbance detector at 500 nm and an ELSD are provided in FIGS. 8 and 9,respectively. The upward shift of the baseline for the last peak in FIG.9 is due to the low volatility of cyclohexanone in the ELSD detector. Acomparison of the relative peak areas for the three asphaltene peaks(cyclohexane, toluene, and cyclohexanone) are provided in Table 5.

Separation profiles for 10 uL of 20 wt. % unpyrolyzed Boscan residuum inmethylene chloride with methylene chloride as the fourth solvent usingan absorbance detector at 500 nm and an ELSD are provided in FIGS. 10and 11, respectively. A comparison of the relative peak areas for thethree asphaltene peaks (cyclohexane, toluene, and cyclohexanone) areprovided in Table 6.

It is interesting to note that even the unpyrolyzed residua each containa small portion of the fourth peak, which represents the most polarheptane insoluble material. As pyrolysis progresses, the least polarportion of asphaltenes (cyclohexane soluble) decreases, while the mostpolar portion (cyclohexanone or methylene chloride soluble) increases(FIGS. 12 and 13). The relative amount of the intermediate polaritymaterial (toluene soluble) drops slowly. Presumably the least polarmaterial passes through a stage of intermediate polarity, which thengenerates the more polar “pre-coke” material. There is a dramaticincrease in the relative amount of the most polar component for the75-minute pyrolyzed Redwater, B.C. material, as coke begins to form.

The total asphaltenes peak areas are listed in Table 5 for thecyclohexanone separations and in Table 6 for the methylene chlorideseparations. The total areas of the three asphaltene peaks (cyclohexanesoluble, toluene soluble, and cyclohexanone or methylene chloridesoluble) are plotted against the gravimetric heptane asphaltene contentin FIGS. 14 and 15. As with the three-solvent profile in FIG. 7, theELSD data show a more severe plateau than the 500 nm data for theseverely pyrolyzed oils. This is not due to the deposition of pre-cokematerial onto the PTFE stationary phase, since the last solventcompletely dissolves this material. The plateau profiles in FIGS. 14 and15 with the ELSD detector indicate that the gravimetric separation ofheptane insolubles provides a different result from the on-columnprecipitation and re-dissolution experiment. The on-column separationprovides more detail on the interior structure of the most polarcomponents of residua than a simple gravimetric procedure. Thegravimetric separation appears to provide some additional mass which isnot accounted for in the on-column separation. The plateau observed withthe ELSD for the same separation is not as evident with the 500 nmabsorbance detector. This is probably a coincidence which is due to theincrease in absorptivity for the pyrolyzed asphaltenes material at 500nm compared with the unpyrolyzed material. The correlation betweenasphaltene peak areas and gravimetric asphaltenes content does not takeinto account the area of the maltenes peaks for the various samples,since with this separation, the maltenes peak is off-scale for 2 mginjections. The use of smaller injections to provide a total peak area(maltenes and asphaltenes) to provide data to correlate with gravimetricasphaltenes content is described in a subsequent section.

A New Stability Gauge:

A new parameter that can provide insight into the degree of stability ofa petroleum material can be defined from the results of this work. Thisis the ratio of the peak area for the cyclohexane soluble asphaltenespeak to the cyclohexanone or methylene chloride soluble asphaltenes peakarea from the on-column precipitation and re-dissolution profile. Theratios for both solvents using both 500 nm absorbance and ELSD detectorsare provided in Table 7. The ratios decrease dramatically withincreasing pyrolysis times. Based on these values, threshold valuescould be established for a particular detector and solvent series usedfor the separation. The separation could be used as a sensitive tool todiagnose the severity of pyrolysis to which a heavy oil material hasbeen subjected. It also can be used as a rapid means for analyzingsamples for refinery distillation process control, to determine theactual “reserve pyrolysis capacity” of a residuum. These numericalresults, as with perhaps all numerical results relative to a specificcolumn, are characteristic of a particular PTFE-packed column, and theymay vary somewhat for a different PTFE-packed column.

Four Solvent Separation Results With Heptane Asphaltenes:

Portions of heptane asphaltenes obtained from the gravimetric procedurewere injected onto the column using the four-solvent step gradientprocedure, using methylene chloride as the fourth solvent. The amountsinjected corresponded to the amounts of asphaltenes that would bepresent in two milligrams of whole residua sample, based on thegravimetric separation. A blank separation is shown in FIG. 16. The ELSDseparation profile for 0.38 mg heptane asphaltenes from unpyrolyzedBoscan residuum is presented in FIG. 17. The ELSD peaks in the blankseparation are due to the step gradient solvent changes. As mentioned inthe Experimental Section, ELSD peak areas for the blanks were subtractedfrom the sample areas. The blank corrected sample areas are provided inTable 16. The blank peaks are near in size to some of the sample peaks,which makes an exact calculation of sample areas somewhat difficult. Acomparison between the asphaltene peak areas and relative peak areasfrom whole samples show that the gravimetric asphaltenes peaks ingeneral have a lower total area in Table 8 (gravimetric) than thecorresponding total asphaltene peak areas for the whole residuaseparations listed in Table 6. Also, the gravimetric asphaltenes (Table8) are relatively deficient in the content of cyclohexane solubleportions relative to the polar materials from the whole sampleseparations (Table 6). Therefore, the gravimetric and on-columnseparations provide different results. The gravimetric separationappears to leave more polar material in solution with the maltenes thanthe on-column separation. This is possibly due to the presence ofassociated complexes, which retain polar materials in solution duringthe gravimetric procedure. Possibly the associated complexes are brokenapart in solutions with methylene chloride, which are injected on to thePTFE column and precipitated with the heptane mobile phase. Methylenechloride appears to be able to break up the associated complexesefficiently, and the individual molecules are possibly in true solution.As to precipitation, the insoluble molecules appear to coat onto thestationary phase (e.g., see 44 (showing ground PTFE on whichprecipitated material is coated) and 45 (showing coated lattice)). Forsolid materials, entropy of solution is not evident. Then, as themolecules coated onto the PTFE surface are exposed to solvents ofincreasing polarity, they are dissolved from the solid surface based onenthalpic solubility parameter interactions, and they go into solution.Possibly in this case, the separation is based more on an individualmolecular level than by associated complexes. This aspect needs to beexplored further. If this is the case, the on-column separation providesa more distinct profile of the non-polar and polar material distributionin petroleum materials than does the gravimetric asphaltene procedure.These numerical results are characteristic of a particular PTFE-packedcolumn, and they may vary somewhat for a different PTFE-packed column.

Two Solvent Separation for the Determination of Asphaltenes:

To provide a correlation between the on-column precipitation method andgravimetric determination of asphaltenes, separations of methylenechloride solutions of the original and pyrolyzed residua were conductedusing a two-solvent step gradient using heptane and methylene chloride.Portions of 0.5 mg of samples were injected to provide both peaks onscale with the ELSD detector (FIG. 18). Small portions of 0.5 mg sampleare not useful if the four-solvent separation is used, because the polarpeaks are in many cases smaller than the corresponding blank peaks, andquantitation becomes inaccurate. For the two solvent separations, thetwo peaks are sufficiently large that this is not an issue. The twopeaks represent the heptane soluble non-polar material, and all theremaining polar material, which is fully soluble in methylene chloride.Since the ELSD response is based on number of molecules, an areacorrection is required in order to convert peak area percent into weightpercent. This was accomplished by comparing the average response forgravimetric asphaltenes (Table 8) to the average response to gravimetricmaltenes (Table 9). The ratio of the two response factors is 1.4, whichis approximately related to the ratio of the density of the polarasphaltenes to the density of the maltenes.

Weight percents of polar materials calculated from the two solventseparations using the ELSD detector are listed in Table 9. Weightpercents of asphaltenes from the gravimetric procedure are plottedagainst weight percents of ELSD asphaltenes from the two columnseparation in FIG. 19. The plot shows that for the particularPTFE-packed column used, there is a critical amount of polar materialrequired, near 18 wt. %, before gravimetric asphaltenes appear. Thereare four points near the top of the line that are off of the line to theright. These represent the unpyrolyzed and 10-minute pyrolyzed Boscanresiduum, and the unpyrolyzed Lloydminster and MaxCL2 residua. Theasphaltenes from these materials possibly are highly associated and havesignificant low polarity solvation shells, so they exhibit enhancedsolubility in the gravimetric separation than would be expected from theELSD correlation line. If these four points, and the points for thethree maltenes at y=0 are excluded from linear regression analysis, thecorrelation coefficient for the line is 0.971, with a slope of 1.24 anda y-intercept of −22.5.

SOME CONCLUSIONS FROM EXPERIMENTS

Experimental conditions for a new rapid, automated on-columnprecipitation and re-dissolution method for examining the polarcomponents of original and pyrolyzed residua have been developed. Theratio of ELSD areas of the least polar asphaltene components(cyclohexane soluble) to the most polar components (cyclohexanone ormethylene chloride soluble) provides a sensitive indicator of the degreeof thermal treatment that the sample has undergone. Total weight percentof polar materials can be determined by a two-solvent method, and thepolar material can be further separated into three fractions ofincreasing polarity using a four-solvent method. Methods based on thenew on-column precipitation and re-dissolution separation technique canprovide significantly more information about the polar components inpetroleum material than the determination of gravimetric asphaltenes.The technique could be scaled up to provide a process for removing themost polar, refractory components from petroleum materials forsubsequent processing or use.

TABLE 1 Data for Original Vacuum Residua and Atmospheric PyrolysisBottoms Pyrolysis time Wt. % C7 Wt. % Wt. % Wt % Toluene Residuum @ 400°C., min Asphaltenes CyC6 Sol. K_(S) Distillate Insolubles (TI) Boscan 017.7 38.5 1.6 na <0.1 10 17.8 31.6 1.5 3.9 <0.1 15 19.0 26.8 1.4 13.4<0.1 20 20.2 28.7 1.4 10.5 <0.1 35 24.4 15.4 1.2 19.5 <0.1 50 28.6 12.31.1 26.1 0.1 90 16.5 6.0 1.0 39.3 23.8 MaxCL2 0 17.0 37.8 1.6 na <0.1 1519.3 32.8 1.5 4.8 <0.1 20 23.3 21.9 1.3 5.9 <0.1 35 22.9 19.5 1.2 11.7<0.1 40 26.6 16.6 1.2 12.1 <0.1 50 26.3 15.8 1.2 16.8 <0.1 Lloydminster0 16.9 47.7 1.9 na <0.1 15 15.9 28.6 1.4 7.6 <0.1 20 18.1 28.2 1.4 12.2<0.1 35 19.6 16.9 1.2 16.5 <0.1 40 21.0 25.4 1.3 19.5 <0.1 60 23.0 13.01.1 24.5 <0.1 Redwater, B.C. 0 8.9 37.9 1.6 na <0.1 25 13.1 27.1 1.4 6.3<0.1 35 14.0 21.6 1.3 8.2 <0.1 50 17.0 22.2 1.3 12.9 <0.1 55 16.4 19.01.2 13.2 <0.1 75 19.3 16.0 1.2 18.7 1.1

TABLE 2 K_(S) Data for Original Vacuum Residua and Atmospheric PyrolysisBottoms On-Column Three-Solvent Area Percent Pyrolysis time WeightPercent 500 nm ELSD Residuum @ 400° C., min CyC6 Sol. K_(S) CyC6 Sol.K_(S) CyC6 Sol. K_(S) Boscan  0 37.4 1.63 28.3, 29.1 1.60 33.3, 33.11.50 10 31.6 1.46 24.6 1.32 31.4 1.46 15 26.8 1.37 20.7 1.26 26.8 1.3720 28.7 1.40 16.8, 18.7 1.22 21.8, 22.0 1.28 35 15.4 1.18 9.14 1.10 17.71.21 50 12.3 1.14 1.57 1.02  2.0 1.02 90 (23.8% TI) 6.0 1.0 — — — —MaxCL2  0 35.2 1.61 31.9 1.54 39.0 1.64 15 32.8 1.49 20.1 1.25 25.4 1.3420 21.9 1.28 16.1, 17.6 1.20 20.1, 21.0 1.26 35 19.5 1.24 12.1 1.14 20.11.25 40 16.6 1.20 10.5 1.12 18.2 1.22 50 15.8 1.19 7.74 1.08 16.4 1.20Lloydminster  0 43.3 1.91 35.9 1.76 43.1 1.76 15 28.6 1.40 23.1 1.3031.5 1.46 20 28.2 1.39 18.0 1.22 24.6 1.33 35 16.9 1.20 11.9 1.14 21.21.27 40 25.4 1.34 11.6 1.13 21.4 1.27 60 13.0 1.15 6.30 1.07 16.4 1.20Redwater, B.C.  0 34.4 1.61 33.7 1.52 45.5 1.83 25 27.1 1.37 21.6 1.2833.8 1.51 35 21.6 1.28 18.4 1.22 30.0 1.43 50 22.2 1.28 13.0 1.15 23.21.30 55 19.0 1.23 12.0 1.13 22.6 1.29 75 (1.1% TI) 16.0 1.24 8.23 1.0821.6 1.28

TABLE 3 Heptane Asphaltenes Data for Original Vacuum Residua andAtmospheric Pyrolysis Bottoms Three-solvent on-column Pyrolysisseparation time Weight Total Asphaltenes @ 400° C., Percent Peak Area,counts × 10⁶ Residuum min Asphaltenes 500 nm ELSD Boscan  0 17.7 16.4,16.9 20.3, 20.3 10 17.8 21.5 19.3 15 19.0 24.2 19.5 20 20.2 24.5, 22.919.3, 18.0 35 24.4 30.9 22.9 50 28.6 32.1 20.9 90 16.5 — — (23.8% TI)MaxCL2  0 17.0 18.5 20.4 15 19.3 23.2 19.8 20 23.3 23.0, 24.1 19.3, 20.035 22.9 27.1 22.1 40 26.6 28.4 23.5 50 26.3 27.6 22.1 Lloydminster  016.9 13.7 21.7 15 15.9 17.8 18.1 20 18.1 20.7 18.7 35 19.6 23.3 20.6 4021.0 23.5 19.9 60 23.0 25.6 20.6 Redwater,  0  8.9 11.6 12.4 B.C. 2513.1 17.0 13.5 35 14.0 18.8 14.3 50 17.0 21.3 15.8 55 16.4 22.0 16.7 7519.3 24.7 25.6 (1.1% TI)

TABLE 4 Hansen Solubility Parameter Components, MPa^(1/2) (Hansen 2000)Hydrogen Solvent Dispersion Polar Bonding n-Heptane 15.3 0.0 0.0Cyclohexane 16.8 0.0 0.2 Toluene 18.0 1.4 2.0 Toluene:methanol 17.9 1.62.4 (98:2)(v:v) Solvents with solubility parameter components similar tomethylene chloride Methylene Chloride 18.2 6.3 6.1 Cyclohexanone 17.86.3 5.1 Pyridine 19.0 8.8 5.9 Quinoline 19.4 7.0 7.6 Tetrahydrofuran16.8 5.7 8.0

TABLE 5 On-Column Separation with Four Solvents: Heptane, Cyclohexane,Toluene, and Cyclohexanone Total Asphaltenes Relative Asphaltenes PeakAreas Pyrolysis time Peak Area, counts Cyclohexane Toluene Cyclohexanoneat 400° C., min. 500 nm ELSD 500 nm ELSD 500 nm ELSD 500 nm ELSD Boscan 0 18.64 22.12 0.199 0.257 0.668 0.701 0.133 0.042 10 22.76 20.09 0.1430.179 0.685 0.762 0.171 0.059 15 25.25 19.34 0.106 0.143 0.680 0.7610.214 0.096 20 26.08 20.13 0.099 0.135 0.763 0.754 0.102 0.089 35 29.7119.81 0.053 0.091 0.650 0.754 0.298 0.155 50 32.47 19.35 0.030 0.0650.611 0.748 0.359 0.187 MaxCL2  0 20.81 19.75 0.193 0.204 0.659 0.7490.148 0.047 15 23.74 18.21 0.104 0.107 0.699 0.802 0.198 0.091 20 25.1719.44 0.091 0.091 0.700 0.819 0.209 0.091 35 27.21 19.85 0.060 0.0660.695 0.809 0.245 0.124 40 28.70 21.47 0.055 0.068 0.682 0.792 0.2630.139 50 29.64 20.70 0.040 0.053 0.666 0.792 0.295 0.155 Lloydminster  016.13 21.85 0.214 0.239 0.650 0.728 0.136 0.033 15 19.08 16.02 0.1140.123 0.696 0.806 0.190 0.071 20 21.70 17.19 0.088 0.097 0.705 0.8110.207 0.092 35 23.00 16.98 0.064 0.067 0.693 0.813 0.243 0.120 40 24.9218.89 0.057 0.076 0.683 0.780 0.260 0.144 60 25.69 17.44 0.035 0.0400.670 0.807 0.295 0.154 Redwater, B.C.  0 14.99 9.77 0.174 0.187 0.6570.764 0.169 0.049 25 19.01 10.29 0.091 0.095 0.688 0.810 0.221 0.094 3520.59 11.32 0.074 0.096 0.685 0.794 0.241 0.110 50 23.36 11.65 0.0600.083 0.670 0.796 0.271 0.121 55 23.12 14.55 0.051 0.057 0.660 0.7950.290 0.148 75 (coke) 26.13 12.93 0.038 0.038 0.643 0.774 0.320 0.188

TABLE 6 On-Column Separation of 2.0 mg Portions of Whole Residua withFour Solvents: Heptane, Cyclohexane, Toluene, and Methylene ChlorideTotal Asphaltenes Relative Asphaltenes Peak Areas Pyrolysis time PeakArea, counts Cyclohexane Toluene CH₂Cl₂ at 400° C., min. 500 nm ELSD 500nm ELSD 500 nm ELSD 500 nm ELSD Boscan  0 21.41 23.97 0.096 0.151 0.8100.788 0.094 0.060 10 23.71 19.68 0.068 0.122 0.797 0.783 0.135 0.095 1528.45 21.29 0.050 0.099 0.775 0.767 0.175 0.099 20 27.53 20.95 0.0450.098 0.776 0.768 0.179 0.134 35 29.35 19.73 0.021 0.067 0.720 0.7260.259 0.206 50 31.87 20.25 0.017 0.046 0.680 0.699 0.302 0.254 MaxCL2  019.50 18.90 0.085 0.130 0.786 0.790 0.130 0.080 15 24.19 18.94 0.0490.083 0.769 0.778 0.182 0.139 20 27.16 21.66 0.043 0.088 0.764 0.7610.192 0.151 35 26.67 19.64 0.027 0.062 0.732 0.739 0.241 0.199 40 29.8222.38 0.024 0.054 0.700 0.718 0.276 0.228 50 27.66 19.32 0.017 0.0380.693 0.714 0.290 0.248 Lloydminster  0 15.31 20.82 0.090 0.146 0.8080.793 0.102 0.061 15 17.21 14.99 0.044 0.071 0.790 0.809 0.166 0.119 2018.24 15.17 0.033 0.068 0.770 0.785 0.197 0.147 35 18.91 14.84 0.0230.057 0.738 0.754 0.239 0.189 40 21.42 16.76 0.023 0.052 0.714 0.7320.263 0.216 60 21.46 15.46 0.017 0.039 0.698 0.721 0.285 0.240 Redwater,B.C.  0 15.64 12.66 0.084 0.107 0.757 0.798 0.141 0.096 25 17.03 13.170.036 0.145 0.757 0.710 0.206 0.145 35 17.49 11.68 0.029 0.062 0.7400.757 0.231 0.182 50 20.03 13.45 0.024 0.052 0.709 0.729 0.266 0.219 5518.48 11.63 0.022 0.041 0.695 0.720 0.283 0.239 75 (coke) 16.04 10.300.018 0.020 0.650 0.630 0.332 0.450

TABLE 7 Ratio of Areas of the Cyclohexane Soluble Asphaltene Peaks tothe Cyclohexanone-Soluble or Methylene Chloride-Soluble Asphaltene PeaksOn-Column Precipitation and Pyrolysis Re-dissolution Peak Area Ratiostime at Cyclohexane/ Cyclohexane/ 400° C., Cyclohexanone MethyleneChloride min. 500 nm ELSD 500 nm ELSD Boscan  0 1.50 6.11 1.02 2.52 100.84 3.02 0.51 1.29 15 0.49 1.49 0.28 0.74 20 0.46 1.32 0.25 0.73 350.18 0.58 0.08 0.33 50 0.08 0.35 0.06 0.18 MaxCL2  0 1.30 4.38 0.65 1.6215 0.52 1.17 0.27 0.60 20 0.44 1.00 0.23 0.59 35 0.24 0.53 0.11 0.31 400.21 0.49 0.09 0.24 50 0.14 0.34 0.06 0.15 Lloydminster  0 1.58 7.250.88 2.40 15 0.60 1.74 0.27 0.60 20 0.42 1.06 0.17 0.46 35 0.26 0.560.10 0.30 40 0.22 0.53 0.09 0.24 60 0.12 0.26 0.06 0.16 Redwater, B.C. 0 1.03 3.81 0.60 1.12 25 0.41 1.01 0.18 1.00 35 0.31 0.88 0.12 0.34 500.22 0.68 0.09 0.24 55 0.17 0.38 0.08 0.17 75 0.12 0.27 0.05 0.06 (coke)

TABLE 8 On-Column Separation of Gravimetric Heptane Asphaltenes withFour Solvents: Heptane, Cyclohexane, Toluene, and Methylene Chlorideusing ELSD Detector Total Response Pyrolysis time Asphaltene FactorRelative Asphaltenes Peak Areas at 400° C., min. mg^(a) Peak AreaArea/mg Heptane Cyclohexane Toluene CH₂Cl₂ Boscan 0 0.36 13.44 37.3<0.001 0.027 0.788 0.185 15 0.38 11.48 30.2 <0.001 0.031 0.752 0.217 350.49 13.94 28.4 <0.001 0.011 0.661 0.328 50 0.57 14.25 25.0 0.072 0.0260.549 0.354 MaxCL2 0 0.34 13.85 40.7 <0.001 0.019 0.761 0.220 15 0.3915.14 38.8 <0.001 0.034 0.674 0.291 35 0.46 16.75 36.4 <0.001 0.0410.632 0.327 50 0.52 18.11 34.8 0.052 0.017 0.578 0.353 Lloydminster 00.34 13.83 40.7 <0.001 0.025 0.794 0.181 15 0.32 13.86 43.3 <0.001 0.0360.731 0.233 35 0.40 15.57 38.9 <0.001 0.035 0.685 0.281 60 0.46 18.1539.5 0.053 0.033 0.603 0.312 Redwater, B.C. 0 0.18 8.88 49.3 <0.0010.027 0.685 0.288 35 0.28 13.66 48.8 <0.001 0.020 0.663 0.318 55 0.3316.13 48.9 <0.001 0.016 0.635 0.348 75 0.38 19.79 52.1 0.059 0.020 0.5580.363 Average response, area/mg 39.6 Relative standard deviation 19.6%^(a)Corresponds to the amount of gravimetric asphaltenes in 2.0 mgresiduum

TABLE 9 On-Column Separation of 0.50 mg of Whole Residua and ResiduaHeptane Maltenes with Two Solvents: Heptane and Methylene Chloride usingELSD Detector ELSD Response Corrected (x1.4) Pyrolysis time Peak AreaCounts Response Asphaltene at 400° C., min. Maltenes Asphaltenes TotalArea Area/mg Weight Percent Boscan  0 16.85 7.49 24.34 48.7 38.4 1017.77 7.18 24.95 49.9 36.1 15 17.71 6.89 24.60 49.2 35.3 20 18.36 7.4025.76 51.5 36.1 35 19.08 8.32 27.40 54.8 37.9 50 18.80 8.72 27.52 55.039.4 MaxCL2  0 21.57 8.50 30.07 60.1 35.6 15 21.09 8.03 29.12 58.2 34.820 20.44 8.02 28.46 56.9 35.5 35 19.76 8.03 27.79 55.6 36.3 40 18.038.36 26.39 52.8 39.4 50 19.54 9.06 28.60 57.2 39.4 Lloydminster  0 19.197.77 26.96 53.9 36.2 15 20.88 6.55 27.43 54.9 30.5 20 20.06 7.23 27.2954.6 33.5 35 20.09 7.14 27.23 54.5 33.2 40 20.74 8.13 28.87 57.7 35.4 6021.02 8.70 29.72 59.4 36.7 Redwater, B.C.  0 19.53 4.86 24.39 48.8 25.825 19.52 5.52 25.04 50.1 28.3 35 18.75 5.56 24.31 48.6 29.3 50 19.636.50 26.13 52.3 31.2 55 20.70 6.36 27.06 54.1 30.1 75 (coke) 20.48 7.1927.67 55.3 33.0 Average response, area/mg 53.9 Relative standarddeviation 3.5% Unpyrolyzed Maltenes Boscan 24.37 3.04 27.41 54.8 14.9Lloydminster 22.39 5.06 27.45 54.9 24.0 Redwater, B.C. 25.96 4.58 30.5461.1 19.8 Average response, area/mg 56.9 Relative standard deviation3.6%

Additional Information:

As can be easily understood from the foregoing, the basic concepts ofthe present invention may be embodied in a variety of ways. It involvesboth analysis and processing techniques as well as devices to accomplishthe appropriate analysis or processing. In this application, theanalysis and processing techniques are disclosed as part of the resultsshown to be achieved by the various devices described and as steps whichare inherent to utilization. They are simply the natural result ofutilizing the devices as intended and described. In addition, while somedevices are disclosed, it should be understood that these not onlyaccomplish certain methods but also can be varied in a number of ways.Importantly, as to all of the foregoing, all of these facets should beunderstood to be encompassed by this disclosure.

The discussion included in this non-provisional application is intendedto serve as a basic description. The reader should be aware that thespecific discussion may not explicitly describe all embodimentspossible; many alternatives are implicit. It also may not fully explainthe generic nature of the invention and may not explicitly show how eachfeature or element can actually be representative of a broader functionor of a great variety of alternative or equivalent elements. Again,these are implicitly included in this disclosure. Where the invention isdescribed in device-oriented terminology, each element of the deviceimplicitly performs a function. Apparatus claims may not only beincluded for the device described, but also method or process claims maybe included to address the functions the invention and each elementperforms. Neither the description nor the terminology is intended tolimit the scope of the claims that will be included in any subsequentpatent application.

It should also be understood that a variety of changes may be madewithout departing from the essence of the invention. Such changes arealso implicitly included in the description. They still fall within thescope of this invention. A broad disclosure encompassing both theexplicit embodiment(s) shown, the great variety of implicit alternativeembodiments, and the broad methods or processes and the like areencompassed by this disclosure and may be relied upon when drafting theclaims for any subsequent patent application. It should be understoodthat such language changes and broader or more detailed claiming may beaccomplished at a later date (such as by any required deadline) or inthe event the applicant subsequently seeks a patent filing based on thisfiling. With this understanding, the reader should be aware that thisdisclosure is to be understood to support any subsequently filed patentapplication that may seek examination of as broad a base of claims asdeemed within the applicant's right and may be designed to yield apatent covering numerous aspects of the invention both independently andas an overall system.

Further, each of the various elements of the invention and claims mayalso be achieved in a variety of manners. Additionally, when used orimplied, an element is to be understood as encompassing individual aswell as plural structures that may or may not be physically connected.This disclosure should be understood to encompass each such variation,be it a variation of an embodiment of any apparatus embodiment, a methodor process embodiment, or even merely a variation of any element ofthese. Particularly, it should be understood that as the disclosurerelates to elements of the invention, the words for each element may beexpressed by equivalent apparatus terms or method terms—even if only thefunction or result is the same. Such equivalent, broader, or even moregeneric terms should be considered to be encompassed in the descriptionof each element or action. Such terms can be substituted where desiredto make explicit the implicitly broad coverage to which this inventionis entitled. As but one example, it should be understood that allactions may be expressed as a means for taking that action or as anelement which causes that action. Similarly, each physical elementdisclosed should be understood to encompass a disclosure of the actionwhich that physical element facilitates. Regarding this last aspect, asbut one example, the disclosure of a “container” should be understood toencompass disclosure of the act of “containing”—whether explicitlydiscussed or not—and, conversely, were there effectively disclosure ofthe act of “containing”, such a disclosure should be understood toencompass disclosure of a “container” and even a “means for containing”Such changes and alternative terms are to be understood to be explicitlyincluded in the description.

Any acts of law, statutes, regulations, or rules mentioned in thisapplication for patent; or patents, publications, or other referencesmentioned in this application for patent are hereby incorporated byreference. Any priority case(s) claimed by this application is herebyappended and hereby incorporated by reference, to the extent thepriority case is not inconsistent with the disclosure in thisnon-provisional application. In addition, as to each term used it shouldbe understood that unless its utilization in this application isinconsistent with a broadly supporting interpretation, common dictionarydefinitions should be understood as incorporated for each term and alldefinitions, alternative terms, and synonyms such as contained in theRandom House Webster's Unabridged Dictionary, second edition are herebyincorporated by reference. Finally, all references listed in the list ofreferences in the information statement filed with the application arehereby appended and hereby incorporated by reference, however, as toeach of the above, to the extent that such information or statementsincorporated by reference might be considered inconsistent with thepatenting of this/these invention(s) such statements are expressly notto be considered as made by the applicant(s).

Thus, the applicant(s) should be understood to have support to claim andmake a statement of invention to at least: i) each of theanalytical/processing devices as herein disclosed and described, ii) therelated methods disclosed and described, iii) similar, equivalent, andeven implicit variations of each of these devices and methods, iv) thosealternative designs which accomplish each of the functions shown as aredisclosed and described, v) those alternative designs and methods whichaccomplish each of the functions shown as are implicit to accomplishthat which is disclosed and described, vi) each feature, component, andstep shown as separate and independent inventions, vii) the applicationsenhanced by the various systems or components disclosed, viii) theresulting products produced by such systems or components, ix) eachsystem, method, and element shown or described as now applied to anyspecific field or devices mentioned, x) methods and apparatusessubstantially as described hereinbefore and with reference to any of theaccompanying examples, xi) the various combinations and permutations ofeach of the elements disclosed, and xii) each potentially dependentclaim or concept as a dependency on each and every one of theindependent claims or concepts presented.

In addition and as to computer aspects and each aspect amenable toprogramming or other electronic automation, the applicant(s) should beunderstood to have support to claim and make a statement of invention toat least: xii) processes performed with the aid of or on a computer asdescribed throughout the above discussion, xiv) a programmable apparatusas described throughout the above discussion, xv) a computer readablememory encoded with data to direct a computer comprising means orelements which function as described throughout the above discussion,xvi) a computer configured as herein disclosed and described, xvii)individual or combined subroutines and programs as herein disclosed anddescribed, xviii) the related methods disclosed and described, xix)similar, equivalent, and even implicit variations of each of thesesystems and methods, xx) those alternative designs which accomplish eachof the functions shown as are disclosed and described, xxi) thosealternative designs and methods which accomplish each of the functionsshown as are implicit to accomplish that which is disclosed anddescribed, xxii) each feature, component, and step shown as separate andindependent inventions, and xxiii) the various combinations andpermutations of each of the above.

With regard to claims whether now or later presented for examination, itshould be understood that for practical reasons and so as to avoid greatexpansion of the examination burden, the applicant may at any timepresent only initial claims or perhaps only initial claims with onlyinitial dependencies. Support should be understood to exist to thedegree required under new matter laws—including but not limited toEuropean Patent Convention Article 123(2) and United States Patent Law35 USC 132 or other such laws—to permit the addition of any of thevarious dependencies or other elements presented under one independentclaim or concept as dependencies or elements under any other independentclaim or concept. In drafting any claims at any time whether in thisapplication or in any subsequent application, it should also beunderstood that the applicant has intended to capture as full and broada scope of coverage as legally available. To the extent thatinsubstantial substitutes are made, to the extent that the applicant didnot in fact draft any claim so as to literally encompass any particularembodiment, and to the extent otherwise applicable, the applicant shouldnot be understood to have in any way intended to or actuallyrelinquished such coverage as the applicant simply may not have beenable to anticipate all eventualities; one skilled in the art, should notbe reasonably expected to have drafted a claim that would have literallyencompassed such alternative embodiments.

Further, if or when used, the use of the transitional phrase“comprising” is used to maintain the “open-end” claims herein, accordingto traditional claim interpretation. Thus, unless the context requiresotherwise, it should be understood that the term “comprise” orvariations such as “comprises” or “comprising”, are intended to implythe inclusion of a stated element or step or group of elements or stepsbut not the exclusion of any other element or step or group of elementsor steps. Such terms should be interpreted in their most expansive formso as to afford the applicant the broadest coverage legally permissible.

Finally, any claims set forth at any time are hereby incorporated byreference as part of this description of the invention, and theapplicant expressly reserves the right to use all of or a portion ofsuch incorporated content of such claims as additional description tosupport any of or all of the claims or any element or component thereof,and the applicant further expressly reserves the right to move anyportion of or all of the incorporated content of such claims or anyelement or component thereof from the description into the claims orvice-versa as necessary to define the matter for which protection issought by this application or by any subsequent continuation, division,or continuation-in-part application thereof, or to obtain any benefitof, reduction in fees pursuant to, or to comply with the patent laws,rules, or regulations of any country or treaty, and such contentincorporated by reference shall survive during the entire pendency ofthis application including any subsequent continuation, division, orcontinuation-in-part application thereof or any reissue or extensionthereon.

What is claimed is:
 1. A method of determining fouling tendency of ahydrocarbon-containing feedstock comprising the steps of: (a) preparinga liquid sample of said hydrocarbon-containing feedstock, saidhydrocarbon-containing feedstock having asphaltenes that includedifferent asphaltene fractions of different polarity; (b) precipitatingat least some of said asphaltenes from said liquid sample with one ormore precipitants in a chromatographic column; (c) dissolving at leasttwo of said different asphaltene fractions from said precipitatedasphaltenes during a successive dissolution protocol that usesdissolving solvents of increasing strength; (d) eluting said at leasttwo different dissolved asphaltene fractions from said chromatographiccolumn; (e) detecting said at least two eluted fractions with a liquidchromatography detector to generate a detector signal for each saideluted fraction; wherein said step of detecting comprises monitoring theamount of said eluted fractions from said chromatographic column withsaid liquid chromatography detector, and wherein said signal isproportional to the amount of each said eluted fraction, (f) using saidsignals to calculate a percentage of each peak area for a first amountand a second amount of dissolved asphaltenes relative to the total peakareas, wherein the peak areas are derived from the signals, to determinea parameter that relates to fouling tendency of saidhydrocarbon-containing feedstock; and (g) determining said foulingtendency of said hydrocarbon-containing feedstock from said parameter.2. The method of claim 1, wherein the hydrocarbon-containing feedstockcomprises a material selected from the group consisting of oil, crudeoil, asphalt, and a coal-derived product.
 3. The method of claim 1,wherein said step of precipitating comprises the step of precipitatingwith one or more precipitants selected from the group consisting ofiso-octane, pentane, heptane, hexane, and mixtures thereof.
 4. Themethod of claim 1, wherein step (c) comprises: (i) dissolving a firstamount of the precipitated asphaltenes in one or more first dissolvingsolvents having a solubility parameter at least 1 MPa^(0.5) higher thanthe one or more precipitants; (ii) dissolving a second amount of theprecipitated asphaltenes in one or more second dissolving solventshaving a solubility parameter higher than the one or more firstdissolving solvents, wherein the solubility parameter of the one or moresecond dissolving solvents is at least about 21 MPa^(0.5) but no greaterthan about 30 MPa^(0.5).
 5. The method of claim 4, further comprisingprior to step (ii): dissolving at least part of the precipitatedasphaltenes in one or more third dissolving solvents having a solubilityparameter between the solubility parameter of the first dissolvingsolvent and the solubility parameter of the second dissolving solvent;and dissolving at least part of the precipitated asphaltenes in one ormore fourth dissolving solvents having a solubility parameter betweenthe solubility parameter of the third dissolving solvent and thesolubility parameter of the second dissolving solvent.
 6. The method ofclaim 1 wherein said step of monitoring the amount of eluted fractionsfrom the column comprises monitoring the concentration of elutedfractions from the column with a liquid chromatography detector thatgenerates a signal proportional to the concentration of each elutedfraction.
 7. The method of claim 1, wherein step (c) comprisesdissolving a first amount and a second amount of the precipitatedasphaltenes by gradually and continuously changing the solvents to afinal mobile phase solvent having a solubility parameter at least about1 MPa^(0.5) higher than the one or more precipitants.
 8. The method ofclaim 1, wherein step (c) comprises: (i) gradually and continuouslychanging the one or more precipitants to a first final mobile phasedissolving solvent having a solubility parameter at least about 1MPa^(0.5) higher than the one or more precipitants to dissolve a firstamount of the precipitated asphaltenes; and (ii) gradually andcontinuously changing the first final mobile phase dissolving solvent toa second final mobile phase dissolving solvent having a solubilityparameter at least about 1 MPa^(0.5) higher than the first final mobilephase dissolving solvent to dissolve a second amount of the precipitatedasphaltenes.
 9. The method of claim 1 wherein said step of detectingsaid at least two eluted fractions comprises the step of detecting togenerate a separation profile.
 10. The method of claim 1 wherein thefouling tendency is derived from a determination of the amount offoulant deposited.
 11. The method of claim 1 wherein feedstock foulingtendencies are determined thermally treating at least two feedstocks tovarying degrees, then cooling said thermally treated feedstocks, andthen analyzing samples of the feedstocks for high polarity asphalteneconcentration to determine the effect thermally treating the feedstockhas on producing high polarity asphaltenes.
 12. The method of claim 1,wherein said hydrocarbon containing feedstock sample is a firsthydrocarbon containing feedstock sample, and further comprising thesteps of: (h) selecting one or more of the same or differenthydrocarbon-containing feedstock samples; repeating steps (a)-(g); and(i) comparing the parameter of the one or more of the same or differenthydrocarbon-containing feedstock samples with the parameter of the firsthydrocarbon-containing feedstock sample to predict one or more leadingcandidate hydrocarbon-containing feedstocks relative to fouling tendencyduring hydroprocessing.
 13. The method of claim 12 further comprisingthe steps of generating a cost value for the leading candidatehydrocarbon-containing feedstock samples, and comparing the cost valuegenerated for the leading candidate hydrocarbon-containing feedstocksamples with a market price of the same or different hydrocarboncontaining feedstocks.
 14. The method of claim 12, further comprisingthe step of blending the leading candidate hydrocarbon-containingfeedstock with one or more different hydrocarbon-containing feedstocks.15. The method of claim 1, wherein said hydrocarbon containing feedstocksample is a first hydrocarbon containing feedstock sample, and furthercomprising the step of comparing a different sample of the same firsthydrocarbon-containing feedstock sample with the firsthydrocarbon-containing feedstock sample for quality control of the firsthydrocarbon-containing feedstock sample.
 16. The method of claim 1further comprising the steps of generating a cost value for ahydrocarbon-containing feedstock sample, and comparing said cost valuegenerated for said hydrocarbon-containing feedstock sample with a marketprice of the same or different hydrocarbon-containing feedstock.
 17. Themethod of claim 1 further comprising the step of (h) generating a priceof the hydrocarbon-containing feedstock, wherein said method transformsa product development process to reduce time in bringing a product tomarket.
 18. The method of claim 1 wherein said step of precipitating atleast some of said asphaltenes from said liquid sample with one or moreprecipitants in a chromatographic column comprises the step ofprecipitating at least some of said asphaltenes from said liquid samplewith one or more precipitants in a chromatographic column that containsa substantially inert stationary phase.
 19. A method comprising thesteps of: (i) selecting one or more hydrocarbon-containing feedstocks,wherein the selection of the one or more hydrocarbon-containingfeedstocks comprises: (a) preparing a liquid sample of a firsthydrocarbon-containing feedstock, said first hydrocarbon-containingfeedstock having asphaltenes that include different asphaltene fractionsof different polarity; (b) precipitating at least some of saidasphaltenes from said liquid sample with one or more precipitants in achromatographic column; (c) dissolving at least two of said differentasphaltene fractions from said precipitated asphaltenes during asuccessive dissolution protocol that uses dissolving solvents ofincreasing strength; (d) eluting said at least two different dissolvedasphaltene fractions from said chromatographic column; (e) detectingsaid at least two eluted fractions with a detector to generate detectorsignals; (f) using said signals to calculate a percentage of each peakarea for a first amount and a second amount of dissolved asphaltenesrelative to the total peak areas, wherein the peak areas are derivedfrom the signals, to determine a parameter that relates to foulingtendency of said first hydrocarbon-containing feedstock; (g) determiningsaid fouling tendency of said first hydrocarbon-containing feedstockfrom said parameter; and (ii) feeding the selectedhydrocarbon-containing feedstock to one or more crude hydrocarbonrefinery components.
 20. The method of claim 19, further comprising (h)selecting one or more second hydrocarbon-containing feedstock samples;repeating steps (a)-(g); and comparing the parameter for the one or moresecond hydrocarbon-containing feedstock samples with the parameter forthe first hydrocarbon-containing feedstock sample to predict one or moreleading candidate hydrocarbon-containing feedstocks relative to foulingtendency during hydroprocessing.
 21. The method of claim 19, wherein theone or more hydrocarbon refinery components is selected from the groupconsisting of a component used in oil processing, a component used inoil fractionating, a component used in oil production, a pipelinecomponent, a hydrotreating process component, a distillation processcomponent, a vacuum distillation process component, an atmosphericdistillation process component, a visbreaking process component, ablending process component, an asphalt formation process component, anextraction component, a coking onset estimation component, a foulingcomponent, a refinery unit, a heat exchanger, and a refinery unit otherthan a heat exchanger.
 22. The method of claim 19 wherein said step ofprecipitating at least some of said asphaltenes from said liquid samplewith one or more precipitants in a chromatographic column comprises thestep of precipitating at least some of said asphaltenes from said liquidsample with one or more precipitants in a chromatographic column thatcontains a substantially inert stationary phase.
 23. A systemcomprising: (i) one or more crude oil hydrocarbon refinery components;and (ii) one or more hydrocarbon-containing feedstocks in fluidcommunication with the one or more crude hydrocarbon refinerycomponents, wherein the one or more hydrocarbon-containing feedstocks isselected by a process comprising the steps of: (a) preparing a liquidsample of a first hydrocarbon-containing feedstock, said firsthydrocarbon-containing feedstock having asphaltenes that includedifferent asphaltene fractions of different polarity; (b) precipitatingat least some of said asphaltenes from said liquid sample with one ormore precipitants in a chromatographic column; (c) dissolving at leasttwo of said different asphaltene fractions from said precipitatedasphaltenes during a successive dissolution protocol that usesdissolving solvents of increasing strength; (d) eluting said at leasttwo different dissolved asphaltene fractions from said chromatographiccolumn; (e) detecting said at least two eluted fractions with a detectorto generate detector signals; (f) using said signals to calculate apercentage of each peak area for a first amount and a second amount ofdissolved asphaltenes relative to the total peak areas, wherein the peakareas are derived from the signals, to determine a parameter thatrelates to fouling tendency of said hydrocarbon-containing feedstock;and (g) determining the fouling tendency of said firsthydrocarbon-containing feedstock from said parameter.
 24. The system ofclaim 23, wherein the process further comprises (h) selecting one ormore second hydrocarbon-containing feedstock samples; repeating steps(a)-(g); and comparing the parameter for the one or more secondhydrocarbon-containing feedstock samples with the parameter for thefirst hydrocarbon-containing feedstock sample to predict one or moreleading candidate hydrocarbon-containing feedstocks relative to foulingtendency during hydroprocessing.
 25. The system of claim 23, wherein theone or more crude hydrocarbon refinery components is selected from thegroup consisting of a component used in oil processing, a component usedin oil fractionating, a component used in oil production, a pipelinecomponent, a hydrotreating process component, a distillation processcomponent, a vacuum distillation process component, an atmosphericdistillation process component, a visbreaking process component, ablending process component, an asphalt formation process component, anextraction component, a coking onset estimation component, a foulingcomponent, a refinery unit, a heat exchanger, and a refinery unit otherthan a heat exchanger.
 26. The method of claim 24 further comprising thesteps of selecting one or more second hydrocarbon-containing feedstocksamples; repeating steps (i)-(vii); comparing the parameter for the oneor more second hydrocarbon-containing feedstock samples with theparameter for the first hydrocarbon-containing feedstock sample topredict which of the hydrocarbon-containing feedstock samples is aleading candidate relative to fouling tendency during hydroprocessing;and selecting the leading candidate hydrocarbon containing feedstocksbased on fouling tendency of the hydrocarbon containing feedstock forhydroprocessing and price.
 27. The system of claim 23 wherein said stepof precipitating at least some of said asphaltenes from said liquidsample with one or more precipitants in a chromatographic columncomprises the step of precipitating at least some of said asphaltenesfrom said liquid sample with one or more precipitants in achromatographic column that contains a substantially inert stationaryphase.